US3052647A - Heat hardenable composition comprising an alkyd resin, an epoxy polyester resin, anda dipentene:maleic acid anhydride adduct and process of preparing same - Google Patents
Heat hardenable composition comprising an alkyd resin, an epoxy polyester resin, anda dipentene:maleic acid anhydride adduct and process of preparing same Download PDFInfo
- Publication number
- US3052647A US3052647A US759139A US75913958A US3052647A US 3052647 A US3052647 A US 3052647A US 759139 A US759139 A US 759139A US 75913958 A US75913958 A US 75913958A US 3052647 A US3052647 A US 3052647A
- Authority
- US
- United States
- Prior art keywords
- resin
- mixture
- acid anhydride
- polyester resin
- dipentene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000203 mixture Substances 0.000 title claims description 65
- 229920001225 polyester resin Polymers 0.000 title claims description 32
- 239000004645 polyester resin Substances 0.000 title claims description 32
- 239000004593 Epoxy Substances 0.000 title claims description 31
- 229920000180 alkyd Polymers 0.000 title claims description 24
- XMGQYMWWDOXHJM-UHFFFAOYSA-N limonene Chemical compound CC(=C)C1CCC(C)=CC1 XMGQYMWWDOXHJM-UHFFFAOYSA-N 0.000 title description 36
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 title description 18
- 238000000034 method Methods 0.000 title description 17
- -1 HYDROXY GROUPS Chemical group 0.000 claims description 9
- 150000001298 alcohols Chemical class 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 229920005989 resin Polymers 0.000 description 49
- 239000011347 resin Substances 0.000 description 49
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 35
- 239000002253 acid Substances 0.000 description 21
- 239000007859 condensation product Substances 0.000 description 21
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 21
- 239000000306 component Substances 0.000 description 18
- 235000011187 glycerol Nutrition 0.000 description 17
- 239000004848 polyfunctional curative Substances 0.000 description 16
- 150000008064 anhydrides Chemical class 0.000 description 15
- 239000000047 product Substances 0.000 description 15
- 241000428199 Mustelinae Species 0.000 description 9
- 150000007513 acids Chemical class 0.000 description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 9
- 229910052753 mercury Inorganic materials 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- LGRFSURHDFAFJT-UHFFFAOYSA-N phthalic anhydride Chemical compound C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 150000008065 acid anhydrides Chemical class 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical group OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 5
- 238000005266 casting Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 229920000728 polyester Polymers 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- KMOUUZVZFBCRAM-UHFFFAOYSA-N 1,2,3,6-tetrahydrophthalic anhydride Chemical compound C1C=CCC2C(=O)OC(=O)C21 KMOUUZVZFBCRAM-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 4
- 239000011976 maleic acid Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 150000005846 sugar alcohols Polymers 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- WZHHYIOUKQNLQM-UHFFFAOYSA-N 3,4,5,6-tetrachlorophthalic acid Chemical compound OC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(O)=O WZHHYIOUKQNLQM-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000003822 epoxy resin Substances 0.000 description 3
- 150000002148 esters Chemical class 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 3
- 229920000647 polyepoxide Polymers 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- AUHHYELHRWCWEZ-UHFFFAOYSA-N tetrachlorophthalic anhydride Chemical compound ClC1=C(Cl)C(Cl)=C2C(=O)OC(=O)C2=C1Cl AUHHYELHRWCWEZ-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- MFYSUUPKMDJYPF-UHFFFAOYSA-N 2-[(4-methyl-2-nitrophenyl)diazenyl]-3-oxo-n-phenylbutanamide Chemical compound C=1C=CC=CC=1NC(=O)C(C(=O)C)N=NC1=CC=C(C)C=C1[N+]([O-])=O MFYSUUPKMDJYPF-UHFFFAOYSA-N 0.000 description 2
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 150000005840 aryl radicals Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 210000003298 dental enamel Anatomy 0.000 description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000003700 epoxy group Chemical group 0.000 description 2
- 150000002170 ethers Chemical class 0.000 description 2
- QQVIHTHCMHWDBS-UHFFFAOYSA-N isophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1 QQVIHTHCMHWDBS-UHFFFAOYSA-N 0.000 description 2
- 239000004922 lacquer Substances 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- UFDHBDMSHIXOKF-UHFFFAOYSA-N tetrahydrophthalic acid Natural products OC(=O)C1=C(C(O)=O)CCCC1 UFDHBDMSHIXOKF-UHFFFAOYSA-N 0.000 description 2
- NIDNOXCRFUCAKQ-UMRXKNAASA-N (1s,2r,3s,4r)-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1[C@H]2C=C[C@@H]1[C@H](C(=O)O)[C@@H]2C(O)=O NIDNOXCRFUCAKQ-UMRXKNAASA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WVDGHGISNBRCAO-UHFFFAOYSA-N 2-hydroxyisophthalic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=C1O WVDGHGISNBRCAO-UHFFFAOYSA-N 0.000 description 1
- UHMARZNHEMRXQH-UHFFFAOYSA-N 3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical class C1=CCCC2C(=O)OC(=O)C21 UHMARZNHEMRXQH-UHFFFAOYSA-N 0.000 description 1
- BHELIUBJHYAEDK-OAIUPTLZSA-N Aspoxicillin Chemical compound C1([C@H](C(=O)N[C@@H]2C(N3[C@H](C(C)(C)S[C@@H]32)C(O)=O)=O)NC(=O)[C@H](N)CC(=O)NC)=CC=C(O)C=C1 BHELIUBJHYAEDK-OAIUPTLZSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-ONCXSQPRSA-N abietic acid Chemical compound C([C@@H]12)CC(C(C)C)=CC1=CC[C@@H]1[C@]2(C)CCC[C@@]1(C)C(O)=O RSWGJHLUYNHPMX-ONCXSQPRSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- IFDVQVHZEKPUSC-UHFFFAOYSA-N cyclohex-3-ene-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCC=CC1C(O)=O IFDVQVHZEKPUSC-UHFFFAOYSA-N 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- KPDVEXZKUKVGDC-UHFFFAOYSA-N dichloro 3,4,5,6-tetrachlorobenzene-1,2-dicarboxylate Chemical compound ClOC(=O)C1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1C(=O)OCl KPDVEXZKUKVGDC-UHFFFAOYSA-N 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 150000002169 ethanolamines Chemical class 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- CBCIHIVRDWLAME-UHFFFAOYSA-N hexanitrodiphenylamine Chemical compound [O-][N+](=O)C1=CC([N+](=O)[O-])=CC([N+]([O-])=O)=C1NC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O CBCIHIVRDWLAME-UHFFFAOYSA-N 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- ZDCHZHDOCCIZIY-UHFFFAOYSA-N phthalic acid;propane-1,2,3-triol Chemical compound OCC(O)CO.OC(=O)C1=CC=CC=C1C(O)=O ZDCHZHDOCCIZIY-UHFFFAOYSA-N 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000007519 polyprotic acids Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 239000012260 resinous material Substances 0.000 description 1
- 239000012262 resinous product Substances 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- This invention relates to a process for the production of hardened casting resins, making use of liquid or meltable condensation products formed by polyvalent alcohols with polybasic acids and epoxy polyester resinous condensate hardeners.
- liquids or meltable condensation products are well-known resinous materials commonly referred to as alkyd resins or Glyptals, and they have assumed technical importance because it became possible to combine glycerine phthalic acid resins with fatty acids and in this manner to obtain useful and valuable lacquer resins.
- the alkyd resins were found to be rather unsuitable for the production of hardened casting resins, however, because of the impossibility of removing the water produced by the condensation reaction continuously.
- polyglycidyl ethers can be added to polyester resins in order to obtain elastic alkyd resins.
- enamels have been produced by a combination of polyglycidyl ethers of polyvalent phenols with either alkyd resins and polyisocyanates or formaldehyde resins and dicyandiamide.
- liquid or still meltable alkyd resin condensation products formed from polyvalent alcohols with polyvalent carboxylic acids can be transformed in very simple fashion and in a relatively short time into mechanically, thermally and electrically stable high-quality hardened products which are bubble-free and non-shrinking by adding to said condensation products an epoxy polycarboxylic acid ester resin in an amount from 30-70%, preferably 40-60%, of the total mixture, and heating the resulting mixture to temperatures between 60 and 350 C.
- the products are even further improved by the addition of anhydrides of polycarboxylic acids to the mixture of alkyd resin condensation products and epoxy polycarboxylic acid ester resins in an amount from 0-40% of the total mixture.
- the final composition of the hardenable mixture if a two component system, is from 30-70%, preferably 40H60%, epoxyalkyl polyester resin and the remainder alkyd resin; or if a three component system, is from 30-70%, preferably 40-60%, epoxyalkyl polyester resin, -70%, preferably 20-40% alkyd resin and 0-40% preferably 15-35% polycarboxylic acid anhydride.
- the selection of the suitable alkyd resin condensation product depends upon the requirements of the particular intended field of use and the desired properties.
- the alcohol component can consist of saturated and unsaturated aliphatic polyhydric alcohols, such as glycols, glycol ethers, glycerol, pentaerythrite and hexites as well as polyhydric ethanolamines. If dihydric alcohols are used, they are used in mixture with trior higher polyhydric alcohols.
- the alcohol mixture used for the production of the condensation products should consist partially or entirely of trihydric or higher-polyhydric alcohols.
- condensation products of these tri-hydric or higher-polyhydric alcohols and polycarboxylic acids which are commonly referred to in literature as Glyptal resins, contain unreacted secondary hydroxyl groups and are particularly well suited as starting materials within the scope of the present invention, probably because the hardening takes place due to a reaction of the secondary hydroxyl groups of the resin molecule with the epoxy groups of the epoxy polyester resin.
- the acid components of the alkyd resin condensation products may be saturated or unsaturated aliphatic or aromatic diand polycarboxylic acids and their anhydrides.
- examples of such acids are oxalic acid, succinic acid, maleic acid, the adduct formed by anthracene and maleic acid and the various phthalic acids such as orthophthalic acid, isoor meta-phthalic acid, paraor terephthalic acid and their tetrachloro and tetrahydro derivatives, endomethylene tetrahydrophthalic acid and endomethylene hexachlorophthalic acid.
- dicarboxylic acids containing hydroxyl groups such as tartaric acid, citric acid, hydroxy-isophthalic acid, or other benzene hydroxydicarboxylic acids and naphthalene hydroxydicarboxylic acids may be used for the production of the condensation products.
- the preferable acid components of the alkyd resin condensation products are the various phthalic acids and their anhydrides either alone or admixed with other polycarboxylic acids.
- the known resins may also be modified by condensing with monovalent alcohols and saturated or unsaturated mono-carboxylic acids.
- the epoxy polycarboxylic acid ester resins which are added according to the present invention are mixtures of compounds essentially within the structural formula:
- R and R are radicals selected from the group consisting of hydrogen, alkyl and aryl or monovalent aromatic hydrocarbon radicals,
- R and R are bivalent radicals selected from the group consisting of alkylene and arylene or divalent aromatic hydrocarbon radicals, and
- n is an integer from 0 to 10.
- epoxyalkyl polyester resins are produced, for example in accordancewith the process described in German Patent No. 944,995 by reacting a stoichiometric mixture of an alkali metal salt of a dicarboxylic acid and a halogen epoxide in paste-like form in the presence of diluents under mechanical agitation and in the presence of a catalyst at elevated temperature and, if desired, under pressure.
- the above-mentioned epoxy polyester resins in admixture with the liquid or meltable alkyl resin condensation products containing unreacted secondary hydroxyl groups are hardened under elevated temperatures and optionally in the presence of anhydrides of polycarboxylic acids.
- Particularly suitable are the anhydrides of the same acids which form the basis of either the alkyd resin condensation product or of the epoxy polyester resin. The chemical reactions which occur during this hardening phase are not clearly understood.
- the acid anhydrides react, on the one hand, with the reactive groups of the alkyd resin, for example with the hydroxyl or amino groups, if present, and, on the other hand, with those of the epoxy polyester, and that the free hydroxyl groups of the alkyd resin partially and simultaneously react with the epoxy groups of the epoxy polyester.
- the hardening of the mixtures according to the present invention takes place at temperatures of 60 to 350 C., but in general it is sufficient to heat the mixture at temperatures between 100 and 200 C. for a few hours.
- the heating period and the required temperature are individually dependent upon the composition of the condensation product as well as upon the composition of the hardener used, and may be readily determined within the aforesaid limits by those skilled in the art by preliminary experiments.
- the resins obtained by the process according to the present invention exhibit a great mechanical hardness and strength at normal temperatures, and exhibit a formretention capability according to Martens of 80-140 C.
- the process according to the present invention makes it possible for the first time to transform the brittle and technically relatively valueless Glyptal resins in simple fashion into high-quality synthetic resins which are excellently suitable for use as casting and impregnating resins and as coatings for electro-technical purposes and in the machine and apparatus construction field.
- addition adducts formed by maleic acid anhydride and dipentene are used as the anhydride component to assist in the hardening.
- the use of such anhydride addition adducts causes a reduction in the viscosity of the unhardened resinous mixture and increases the crucible period considerably without adversely influencing the Martens strength or the impact resistance of the end product.
- Dipentene is capable of combining with up to 2 mols maleic acid anhydride. Solid resins which are hard at room temperature are formed thereby. These adducts may be admixed with the previously described alkyd and epoxy resin mixture while hot.
- the production of addition compounds formed by maleic acid anhydride and dipentene is known as such. It is accomplished by heating the components to 160-180 C., using an excess of dipentene, if desired.
- the reaction mixture can be sepanated by. vacuum distillation, whereby unreacted components are first removed and various fractions are then separated. At a vacuum of 1-2 mm. mercury at 145- 160 C.
- a product composed of the adduct of 1 mol dipentene and 1 mol maleic acid anhydride passes over, at a higher temperature the adduct of 1 mol dipentene and 2 mols maleic acid anhydride.
- a hard, resilient resin remains behind as the residue.
- the distilled products are preferably employed for the process according to the present invention.
- the first-mentioned reaction product formed by the adduct of 1 mol of maleic acid anhydride and 1 mol dipentene produces the greatest reduction in viscosity and prolongation of the crucible period.
- the addition product formed by the adduct of 2 mols maleic acid anhydride and 1 mol dipentene, or mixtures of the two above-mentioned addition products are highly effective.
- a mixture produced in accordance with Example 7 below from alkyd resin, epoxy resin and anhydride hardener has a viscosity of about 1000 cp. at 100-110 C. and a pourability of up to one hour.
- Example I 296 gm. of phthalic acid anhydride and 148 gm. of glycerine are first heated to 120 C. until a clear solution is formed, and are then slowly heated for a period of 2-3 hours at 180 C. and finally for an additional hour at 210 C., a vacuum of 1-2 mm. mercury is then applied to the mixture for 50 minutes.
- the slightly yellow, clear resin has an acid number of 50; a hydroxyl number of 230; a saponification number of 525; and an average molecular Weight (dioxane) of 410.
- Example II An alkyd resin is produced by condensing 98 g. of maleic acid anhydride, 146 gm. of phthalic acid anhydride, 92 g. of glycerine and 62 gm. of ethylene glycol. These materials are mixed and heated in a round-bottom flask on a liquid bath to 170-180 C. until the acid number drops to below 100. Thereafter, while increasing the temperature to ZOO-210 C., a vacuum of 1-3 mercury is applied to the mixture for 40-60 minutes. A solid, weakly yellow resin is formed. 70 gm. of this resin, 30 gm.
- Example II of maleic acid anhydride and 100 of an epoxy polyester resin as in Example I are admixed with each other, the mixture is fused at 80-100 C. and is poured into molds in which the resin is allowed to remain for 14 hours at 180 C. for purposes of hardening.
- the Martens strength according to Deutsche Industrienormen specification number 53,458 amounts to -110 C. and the impact resistance according to Irish Industrienorrmen specification number 53,453 is 5-10 cm. kg./cm.
- the Deutsche Industrienormen are the German industrial standards corresponding to ASTM standards.
- Example 111 207 gm. of phthalic acid anhydride and 93 gm. of pentaerythrite are heated for 2 hours at C., and the hot mixture is subsequently degassed for 15 minutes under a vacuum of 5 mm. mercury. 50 gm. of this resin and 50 gm. of an epoxy polyester resin as in Example I are mixed and hardened for 14 hours at C. The resulting resin has a Martens strength of 80-85 C. and an impact resistance of 4-6 cm. kg./cm.
- glycerine 100 gm. of terephthalic acid and 180 gm. of glycerine are heated for 2 hours at 240-250 C. Subsequently, the glycerine is distilled off under a vacuum of 1 mm. mercury. 50 gm. of the brownish transparent resin formed were admixed with 30 gm. of phthalic acid anhydride and 100 gm. of an epoxy polyester resin as in Example I and the mixture was hardened at 180 C. for 3 hours. Martens temperatures of 75-80 C. and impact resistances of 18-22 cm. kg./crn. were determined for the product.
- Example V 250 gm. of isophthalic acid and 460 gm. of glycerine are heated to 230 C. over a course of one hour while stirring and approximately 50 gm. of water distilled off. Thereafter, 280 gm. of glycerine were distilled ofl? at 0.5-1 mm. mercury. 300 gm. of a solid resin having an acid number of 2 are obtained. 50 gm. of this resin, 60 gm. of tetrahydrophthalic acid anhydride and 100 gm. of an epoxy polyester resin as in Example I after being hardened for 3 hours at 180 C., produce a hardened resin having a Martens strength around 80 C. and an impact resistance of 15-20 cm. kg./cm.
- Example VI If, in place of the 60 gm. of tetra-hydrophthalic acid anhydride in Example V, 70 gm. of a mixture of equal parts by weight of phthalic acid anhydride and tetrahydrophthalic acid anhydride are used, a hardened resin having a Martens stability around 85-90 C. and the same impact strength are obtained. As a whole, these values remain the same when 80 gm. of a mixture of tetrahydrophthalic acid anhydride and phthalic acid anhydride (122) are used as hardeners.
- Example VII 286 gm. of tetrachlorophthalic acid anhydride and 368 gm. of glycerine were heated to 230 C. and allowed to remain for 2 hours at that temperature. About 20 gm. of water distilled oil. Subsequently, the glycerine was completely distilled oil in a vacuum of a few mm. mercury. A dark, transparent resin, having an acid number of 1,3, a molecular weight of 900-1100, and a thermometer drip point according to G. F. DAlelio (Kunststoffpraktikum, page 181, published by Karl-Hanser-Verlag, Kunststoff, 1952), of more than 140 C., remained behind. 70 gm.
- Example VIII 286 gm. of tetrachlorophthalic acid anhydride, 384 gm. of maleic acid anhydride and 552 gm. of glycerine were heated within a period of 1 hour to 200 C. and the mixture was allowed to stand at that temperature for 2 hours. A vacuum of 0.5 mm. mercury was applied until no more glycerine could be distilled off. A residue of a lightyellow, transparent resin was obtained. 80 gm. of this light-yellow, transparent resin, 70 gm. of a mixture of the anhydrides of phthalic acid and tetrahydrophthalic acid (2:1) and 100 gm.
- Example II of an epoxy polyester resin as in Example I were melted together at 80 C., degassed and hardened for 14 hours at 140 C.
- the hardened resin had a temperature resistance according to Martens of around 80-90 C. and an impact strength of 30-35 cm. kg./cm.
- Example IX 8 parts by weight of the Glyptal resin described in Example VII, formed from glycerine and tetrachlorophthalic acid anhydride, were melted together at -l00 C., accompanied by stirring, with 10 parts by weight of an epoxide resin produced from sodium or-thophthalate and epichlorohydrin in accordance with Example 3 of German Patent No. 944,995 and 7 parts of an adduct of 1 mol of maleic acid anhydride and 1 mol of dipentene, which had been purified by distillation. The mixture was completely degassed in a vacuum of 5-10 mm. mercury. The viscosity of this mixture was 200 cp. at C. The mixture was still pourable after about 10 hours. After a hardening treatment of 8-10 hours at 180 C., the hardened resin exhibited a temperature stability according to Martens of -120 C. and an impact resistance of 15-20 cm. kg./cm.
- a process of hardening alkyd resins wherein the alcohol component is entirely derived from alcohols having at least three hydroxy groups which comprises adding to said resins (1) an epoxy polyester resin having essentially the structural formula wherein R and R are selected from the group consisting of hydrogen, alkyl and aryl radicals, R and R are bivalent radicals selected from the group consisting of alkylene and arylene radicals and n is an integer from 0 to 10 and (2) a dipentenezmaleic acid anhydride adduct hardener, said three components being the sole reactants, and heating the resulting mixture to temperatures of 60 to 350 C. for a time sufiicient to effect hardening.
- polyester resin condensation products formed from glycerine and a phthalic acid which comprises adding to said condensation products (1) an epoxy polyester resin having two glycide moieties and at least one phthalic acid moiety and (2) at dipentene:maleic acid anhydride adduct hardener, said three components being the sole reactants, and heating the resulting mixture to temperatures of 100 to 200 C. for a time sufiicient to effect hardening.
- the process of producing hardened resins which comprises admixing from 20% to 40% by weight of the mixture of a polyester resin condensation product formed from 'glycerine and a phthalic acid, from 40% to 60% by Weight of the mixture of an epoxy polyester resin having two glycide moieties and at least one phthalic acid moiety and from 15% to 35% by weight of the mixture of a dipentenezmaleic acid anhydride adduct hardener, said three components being the sole react-ants, and heating the resulting mixture to temperatures of 100 to 200 C. for a few hours.
- distillation product is the adduct of 1 mol of dipentene with 1 mol of maleic acidtanhydride.
- the process of producing hardened resins which comprises admixing from 20% to 40% by weight of the mixture of a polyester resin condensation product formed from glycerine and tetrachlorophthalic acid, said resin having a thermometer drip point of more than 140 C., an average molecular weight of about 1000 and an acid number of less than 20, 40% to 60% by weight of the mixture of an epoxy polyester having two glycide moieties and at least one phthalic acid moiety and from 15% to 35% by weight of the mixture of the 1 to 1 adduct of dipentene and maleic acid anhydride, said three com ponents being the sole reactants, and heating the resulting mixture to temperatures of 100 to 200 C. for a few hours. 9.
- a heat hardenable resinous composition comprising 1) an alkyd resin wherein the alcohol component is entirely derived from alcohols having at least three hydroxy groups, (2) an epoxy polyester resin having essentially the structural formula wherein R and R are radicals selected from the group consisting of hydrogen, alkyl and aryl radicals, R and R are bivalent radicals selected from the group consisting of alkylene and arylene radicals and n is an integer from to 10, and (3) a dipentene:maleic acid anh dride adduct hardener, said three components being the sole reactants.
- composition of claim 9 wherein said epoxy polyester resin is present in amounts of from 40% to 60% and said anhydride adduct hardener is present in amounts of from to 35 by weight of the hardenalble mixture.
- a heat hardena-ble resinous composition comprising (1) a polyester resin condensation product formed from vglycerine and a phthalic acid, (2) an epoxy polyester resin having moglycide moieties and at least one phthalic acid moiety and (3) a dipentenezmaleic acid anhydride adduct hardener, said three components being the sole reactants.
- a heat hardenable resinous composition comprising from 20% to by weight of the mixture of a polyester resin condensation product formed from glycerine and a phthalic acid, from 40% to by weight of the mixture of an epoxy polyester resin having two glycide moieties and at least one phthalic acid moiety and from 15% to 35% by weight of the mixture of a dipentenezmaleic acid anhydride adduct hardener, said three components being the sole reactants.
- composition of claim 13 wherein said adduct hardener is the distillation product of the condensation having a ratio of 1 mol of dipentene to 1 mol of maleic acid anhydride.
- a heat harden-able resinous composition comprising from 20% to 40% by weight of the mixture of a polyester resin condensation product formed from glycerine and tetrachlorophthalic acid, sa-id resin having a thermometer drip point of more than C., an average molecular Weight of about 1000 and an acid number of less than 20, 40% to 60% by weight of the mixture of an epoxy polyester having two glycide moieties and at least one phthalic acid moiety and from 15% to 35 by weight of the mixture of the 1 to 1 adduct of dipentene and maleic acid anhydride, said three components being the sole reactants.
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polyesters Or Polycarbonates (AREA)
- Epoxy Resins (AREA)
Description
United States Patent HEAT HARDENABLE COMPOSITKON C(BMPRIS- lNG AN ALKYD RESHJ, AN EPQXY PGLYESTER RESIN, AND A DWENTENEzMALEIC ACID AN- HYDRIDE ADDUCT AND PROCESS 0F PREPAR- ING SAME Helmut Pietsch, Geneva, Switzerland, and Rudolf Kohler, Dusseldorf, and Werner Stein, Dusseldorf- Holthausen, Germany, assignors to Henkel & Cie. G.m.b.H., Dusseldorf-Holthausen, Germany, a corporation of Germany No Drawing. Filed Sept. 5, N58, Scr. No. 759,139 Claims priority, application Germany Nov. 22, 1957 16 Claims. (Cl. 26045.4)
This invention relates to a process for the production of hardened casting resins, making use of liquid or meltable condensation products formed by polyvalent alcohols with polybasic acids and epoxy polyester resinous condensate hardeners.
These liquids or meltable condensation products are well-known resinous materials commonly referred to as alkyd resins or Glyptals, and they have assumed technical importance because it became possible to combine glycerine phthalic acid resins with fatty acids and in this manner to obtain useful and valuable lacquer resins.
The alkyd resins were found to be rather unsuitable for the production of hardened casting resins, however, because of the impossibility of removing the water produced by the condensation reaction continuously. For the production of bubble-free plastic castings, it has therefore been proposed to expose the products during the hardening phase, with the aid of heat, to prolonged perio-ds of pressure. Despite these measures, the resulting products retain a certain degree of thermo-plasticity.
It has also been proposed to add "unsaturated dicarboxylic acids, especially maleic acid or its derivatives, to the alkyd resin, whereby vinyl polymerization takes the place of polycondensation during the hardening phase. However, products having a high mechanical strength or temperature stability cannot be obtained in this manner.
It is further known that polyglycidyl ethers can be added to polyester resins in order to obtain elastic alkyd resins. Furthermore, enamels have been produced by a combination of polyglycidyl ethers of polyvalent phenols with either alkyd resins and polyisocyanates or formaldehyde resins and dicyandiamide.
These known resinous products are useful as lacquers or enamels. The hardened resins produced are highly elastic, but they leave much to be desired regarding their mechanical hardness and stability, and are therefore unsuitable for use as casting resins.
We have found that the liquid or still meltable alkyd resin condensation products formed from polyvalent alcohols with polyvalent carboxylic acids can be transformed in very simple fashion and in a relatively short time into mechanically, thermally and electrically stable high-quality hardened products which are bubble-free and non-shrinking by adding to said condensation products an epoxy polycarboxylic acid ester resin in an amount from 30-70%, preferably 40-60%, of the total mixture, and heating the resulting mixture to temperatures between 60 and 350 C. The products are even further improved by the addition of anhydrides of polycarboxylic acids to the mixture of alkyd resin condensation products and epoxy polycarboxylic acid ester resins in an amount from 0-40% of the total mixture. The final composition of the hardenable mixture; if a two component system, is from 30-70%, preferably 40H60%, epoxyalkyl polyester resin and the remainder alkyd resin; or if a three component system, is from 30-70%, preferably 40-60%, epoxyalkyl polyester resin, -70%, preferably 20-40% alkyd resin and 0-40% preferably 15-35% polycarboxylic acid anhydride.
The selection of the suitable alkyd resin condensation product, which has been produced in accordance with known methods, depends upon the requirements of the particular intended field of use and the desired properties. The alcohol component can consist of saturated and unsaturated aliphatic polyhydric alcohols, such as glycols, glycol ethers, glycerol, pentaerythrite and hexites as well as polyhydric ethanolamines. If dihydric alcohols are used, they are used in mixture with trior higher polyhydric alcohols. The alcohol mixture used for the production of the condensation products should consist partially or entirely of trihydric or higher-polyhydric alcohols. The condensation products of these tri-hydric or higher-polyhydric alcohols and polycarboxylic acids, which are commonly referred to in literature as Glyptal resins, contain unreacted secondary hydroxyl groups and are particularly well suited as starting materials within the scope of the present invention, probably because the hardening takes place due to a reaction of the secondary hydroxyl groups of the resin molecule with the epoxy groups of the epoxy polyester resin.
The acid components of the alkyd resin condensation products may be saturated or unsaturated aliphatic or aromatic diand polycarboxylic acids and their anhydrides. Examples of such acids are oxalic acid, succinic acid, maleic acid, the adduct formed by anthracene and maleic acid and the various phthalic acids such as orthophthalic acid, isoor meta-phthalic acid, paraor terephthalic acid and their tetrachloro and tetrahydro derivatives, endomethylene tetrahydrophthalic acid and endomethylene hexachlorophthalic acid. Similarly, dicarboxylic acids containing hydroxyl groups, such as tartaric acid, citric acid, hydroxy-isophthalic acid, or other benzene hydroxydicarboxylic acids and naphthalene hydroxydicarboxylic acids may be used for the production of the condensation products. The preferable acid components of the alkyd resin condensation products are the various phthalic acids and their anhydrides either alone or admixed with other polycarboxylic acids. The known resins may also be modified by condensing with monovalent alcohols and saturated or unsaturated mono-carboxylic acids.
The epoxy polycarboxylic acid ester resins which are added according to the present invention are mixtures of compounds essentially within the structural formula:
OOG.R4.000.R3.GR2.0H.R1
wherein R and R are radicals selected from the group consisting of hydrogen, alkyl and aryl or monovalent aromatic hydrocarbon radicals,
R and R are bivalent radicals selected from the group consisting of alkylene and arylene or divalent aromatic hydrocarbon radicals, and
n is an integer from 0 to 10.
These epoxyalkyl polyester resins are produced, for example in accordancewith the process described in German Patent No. 944,995 by reacting a stoichiometric mixture of an alkali metal salt of a dicarboxylic acid and a halogen epoxide in paste-like form in the presence of diluents under mechanical agitation and in the presence of a catalyst at elevated temperature and, if desired, under pressure.
The above-mentioned epoxy polyester resins in admixture with the liquid or meltable alkyl resin condensation products containing unreacted secondary hydroxyl groups are hardened under elevated temperatures and optionally in the presence of anhydrides of polycarboxylic acids. Particularly suitable are the anhydrides of the same acids which form the basis of either the alkyd resin condensation product or of the epoxy polyester resin. The chemical reactions which occur during this hardening phase are not clearly understood. It is suspected that the acid anhydrides react, on the one hand, with the reactive groups of the alkyd resin, for example with the hydroxyl or amino groups, if present, and, on the other hand, with those of the epoxy polyester, and that the free hydroxyl groups of the alkyd resin partially and simultaneously react with the epoxy groups of the epoxy polyester.
However, it is also possible that hardening takes place due to a cross-linking esterification as can be observed in the case of the alkyd resins formed from pentaerythrite and hexite. These resins harden in admixture with an epoxy polyester resin by mere heating of the mixture and without the addition of an acid anhydride.
The hardening of the mixtures according to the present invention takes place at temperatures of 60 to 350 C., but in general it is sufficient to heat the mixture at temperatures between 100 and 200 C. for a few hours. The heating period and the required temperature are individually dependent upon the composition of the condensation product as well as upon the composition of the hardener used, and may be readily determined within the aforesaid limits by those skilled in the art by preliminary experiments.
The resins obtained by the process according to the present invention exhibit a great mechanical hardness and strength at normal temperatures, and exhibit a formretention capability according to Martens of 80-140 C. Thus, the process according to the present invention makes it possible for the first time to transform the brittle and technically relatively valueless Glyptal resins in simple fashion into high-quality synthetic resins which are excellently suitable for use as casting and impregnating resins and as coatings for electro-technical purposes and in the machine and apparatus construction field.
The properties of these resins can be further improved if, according to a preferred embodiment of the present invention, addition adducts formed by maleic acid anhydride and dipentene are used as the anhydride component to assist in the hardening. The use of such anhydride addition adducts causes a reduction in the viscosity of the unhardened resinous mixture and increases the crucible period considerably without adversely influencing the Martens strength or the impact resistance of the end product. The resinous mixtures produced containing these anhydride addition products are capable of penetrating the smallest hollow spaces and crevices because of their low viscosity and long crucible period. Moreover, they can be handled in a vacuum without bub- =ble formation. For this reason, they are particularly well suited, for example, for impregnating coils and condensers.
Dipentene is capable of combining with up to 2 mols maleic acid anhydride. Solid resins which are hard at room temperature are formed thereby. These adducts may be admixed with the previously described alkyd and epoxy resin mixture while hot. The production of addition compounds formed by maleic acid anhydride and dipentene is known as such. It is accomplished by heating the components to 160-180 C., using an excess of dipentene, if desired. The reaction mixture can be sepanated by. vacuum distillation, whereby unreacted components are first removed and various fractions are then separated. At a vacuum of 1-2 mm. mercury at 145- 160 C. a product composed of the adduct of 1 mol dipentene and 1 mol maleic acid anhydride passes over, at a higher temperature the adduct of 1 mol dipentene and 2 mols maleic acid anhydride. A hard, resilient resin remains behind as the residue. The distilled products are preferably employed for the process according to the present invention. The first-mentioned reaction product formed by the adduct of 1 mol of maleic acid anhydride and 1 mol dipentene produces the greatest reduction in viscosity and prolongation of the crucible period. Similarly, the addition product formed by the adduct of 2 mols maleic acid anhydride and 1 mol dipentene, or mixtures of the two above-mentioned addition products, are highly effective. Thus, for example, a mixture produced in accordance with Example 7 below from alkyd resin, epoxy resin and anhydride hardener has a viscosity of about 1000 cp. at 100-110 C. and a pourability of up to one hour. If, instead of a mixture of phthalic acid and tetrahydrophthalic acid anhydrides as anhydride hardeners, the same amount of the addition product formed by the adduct of 1 mol maleic acid anhydride and 1 mol of dipentene is added to the mixture as an anhydride hardener, the viscosity decreases to 100-300 cp. at the same temperature and the mixture has a pourability up to 12 hours.
The following examples will further illustrate the present invention and enable others skilled in the art to understand it more completely. It will be understood, however, that the invention is not limited to these particular examples.
Example I 296 gm. of phthalic acid anhydride and 148 gm. of glycerine are first heated to 120 C. until a clear solution is formed, and are then slowly heated for a period of 2-3 hours at 180 C. and finally for an additional hour at 210 C., a vacuum of 1-2 mm. mercury is then applied to the mixture for 50 minutes. The slightly yellow, clear resin has an acid number of 50; a hydroxyl number of 230; a saponification number of 525; and an average molecular Weight (dioxane) of 410.
35 gm. of this resin, 35 gm. of phthalic acid anhydride and 100 gm. of an epoxy polyester resin produced from sodium orthophthalate and epichlorohydrin, in accordance with Example 3 of German Patent No. 944,995, upon being hardened for 10 hours at 140 C. produce a solid resin having a temperature stability of -95 C. and an impact resistance of 15-20 cm. kg./cm.
Example II An alkyd resin is produced by condensing 98 g. of maleic acid anhydride, 146 gm. of phthalic acid anhydride, 92 g. of glycerine and 62 gm. of ethylene glycol. These materials are mixed and heated in a round-bottom flask on a liquid bath to 170-180 C. until the acid number drops to below 100. Thereafter, while increasing the temperature to ZOO-210 C., a vacuum of 1-3 mercury is applied to the mixture for 40-60 minutes. A solid, weakly yellow resin is formed. 70 gm. of this resin, 30 gm. of maleic acid anhydride and 100 of an epoxy polyester resin as in Example I are admixed with each other, the mixture is fused at 80-100 C. and is poured into molds in which the resin is allowed to remain for 14 hours at 180 C. for purposes of hardening. The Martens strength according to Deutsche Industrienormen specification number 53,458 amounts to -110 C. and the impact resistance according to Deutsche Industrienorrmen specification number 53,453 is 5-10 cm. kg./cm. The Deutsche Industrienormen are the German industrial standards corresponding to ASTM standards.
Example 111 207 gm. of phthalic acid anhydride and 93 gm. of pentaerythrite are heated for 2 hours at C., and the hot mixture is subsequently degassed for 15 minutes under a vacuum of 5 mm. mercury. 50 gm. of this resin and 50 gm. of an epoxy polyester resin as in Example I are mixed and hardened for 14 hours at C. The resulting resin has a Martens strength of 80-85 C. and an impact resistance of 4-6 cm. kg./cm.
100 gm. of terephthalic acid and 180 gm. of glycerine are heated for 2 hours at 240-250 C. Subsequently, the glycerine is distilled off under a vacuum of 1 mm. mercury. 50 gm. of the brownish transparent resin formed were admixed with 30 gm. of phthalic acid anhydride and 100 gm. of an epoxy polyester resin as in Example I and the mixture was hardened at 180 C. for 3 hours. Martens temperatures of 75-80 C. and impact resistances of 18-22 cm. kg./crn. were determined for the product.
Example V 250 gm. of isophthalic acid and 460 gm. of glycerine are heated to 230 C. over a course of one hour while stirring and approximately 50 gm. of water distilled off. Thereafter, 280 gm. of glycerine were distilled ofl? at 0.5-1 mm. mercury. 300 gm. of a solid resin having an acid number of 2 are obtained. 50 gm. of this resin, 60 gm. of tetrahydrophthalic acid anhydride and 100 gm. of an epoxy polyester resin as in Example I after being hardened for 3 hours at 180 C., produce a hardened resin having a Martens strength around 80 C. and an impact resistance of 15-20 cm. kg./cm.
Example VI If, in place of the 60 gm. of tetra-hydrophthalic acid anhydride in Example V, 70 gm. of a mixture of equal parts by weight of phthalic acid anhydride and tetrahydrophthalic acid anhydride are used, a hardened resin having a Martens stability around 85-90 C. and the same impact strength are obtained. As a whole, these values remain the same when 80 gm. of a mixture of tetrahydrophthalic acid anhydride and phthalic acid anhydride (122) are used as hardeners.
Example VII 286 gm. of tetrachlorophthalic acid anhydride and 368 gm. of glycerine were heated to 230 C. and allowed to remain for 2 hours at that temperature. About 20 gm. of water distilled oil. Subsequently, the glycerine was completely distilled oil in a vacuum of a few mm. mercury. A dark, transparent resin, having an acid number of 1,3, a molecular weight of 900-1100, and a thermometer drip point according to G. F. DAlelio (Kunststoffpraktikum, page 181, published by Karl-Hanser-Verlag, Munich, 1952), of more than 140 C., remained behind. 70 gm. of this resin, 80 gm. of a mixture of the anhydrides of phthalic acid and tetrahydropht-halic acid (2:1), and 100 gm. of an epoxy polyester resin as in Example I were melted together, degassed in a vacuum accompanied by stirring and then hardened in molds for 12 hours at 180 C. The hardened resin formed thereby has a temperature resistance of 95-105 C. and an impact strength of 15-20 cm. kg./cm. The same result was obtained when 80 gm. of the above tetrachlorophthalic acid Glyptal were used instead of 70 gm.
Example VIII 286 gm. of tetrachlorophthalic acid anhydride, 384 gm. of maleic acid anhydride and 552 gm. of glycerine were heated within a period of 1 hour to 200 C. and the mixture was allowed to stand at that temperature for 2 hours. A vacuum of 0.5 mm. mercury was applied until no more glycerine could be distilled off. A residue of a lightyellow, transparent resin was obtained. 80 gm. of this light-yellow, transparent resin, 70 gm. of a mixture of the anhydrides of phthalic acid and tetrahydrophthalic acid (2:1) and 100 gm. of an epoxy polyester resin as in Example I were melted together at 80 C., degassed and hardened for 14 hours at 140 C. The hardened resin had a temperature resistance according to Martens of around 80-90 C. and an impact strength of 30-35 cm. kg./cm.
Example IX 8 parts by weight of the Glyptal resin described in Example VII, formed from glycerine and tetrachlorophthalic acid anhydride, were melted together at -l00 C., accompanied by stirring, with 10 parts by weight of an epoxide resin produced from sodium or-thophthalate and epichlorohydrin in accordance with Example 3 of German Patent No. 944,995 and 7 parts of an adduct of 1 mol of maleic acid anhydride and 1 mol of dipentene, which had been purified by distillation. The mixture was completely degassed in a vacuum of 5-10 mm. mercury. The viscosity of this mixture was 200 cp. at C. The mixture was still pourable after about 10 hours. After a hardening treatment of 8-10 hours at 180 C., the hardened resin exhibited a temperature stability according to Martens of -120 C. and an impact resistance of 15-20 cm. kg./cm.
While we have disclosed various specific embodiments of our invention, it will be apparent to persons skilled in the art that the present invention is not limited to these specific embodiments and that various changes and modifioations may be made without departing from the spirit of the invention or the scope or the appended claims.
We claim:
1. A process of hardening alkyd resins wherein the alcohol component is entirely derived from alcohols having at least three hydroxy groups which comprises adding to said resins (1) an epoxy polyester resin having essentially the structural formula wherein R and R are selected from the group consisting of hydrogen, alkyl and aryl radicals, R and R are bivalent radicals selected from the group consisting of alkylene and arylene radicals and n is an integer from 0 to 10 and (2) a dipentenezmaleic acid anhydride adduct hardener, said three components being the sole reactants, and heating the resulting mixture to temperatures of 60 to 350 C. for a time sufiicient to effect hardening.
2. The process of claim 1 wherein said epoxy polyester resin is present in amounts of from 40% to 60% by weight of the hardenable mixture.
3. The process of claim 1 wherein said epoxy p-olyester resin is present in amounts of from 40% to 60% and said anhydride adduct hardener is present in amounts of from 15 to 35% by weight of the hardenable mixture.
4. The process of hardening polyester resin condensation products formed from glycerine and a phthalic acid which comprises adding to said condensation products (1) an epoxy polyester resin having two glycide moieties and at least one phthalic acid moiety and (2) at dipentene:maleic acid anhydride adduct hardener, said three components being the sole reactants, and heating the resulting mixture to temperatures of 100 to 200 C. for a time sufiicient to effect hardening.
5. The process of producing hardened resins which comprises admixing from 20% to 40% by weight of the mixture of a polyester resin condensation product formed from 'glycerine and a phthalic acid, from 40% to 60% by Weight of the mixture of an epoxy polyester resin having two glycide moieties and at least one phthalic acid moiety and from 15% to 35% by weight of the mixture of a dipentenezmaleic acid anhydride adduct hardener, said three components being the sole react-ants, and heating the resulting mixture to temperatures of 100 to 200 C. for a few hours.
6. The process of claim 5 wherein said adduct hardener is the distillation product of the condensation of dipentene and maleic acid anhydride.
7. The process of claim 6 wherein said distillation product is the adduct of 1 mol of dipentene with 1 mol of maleic acidtanhydride.
8. The process of producing hardened resins which comprises admixing from 20% to 40% by weight of the mixture of a polyester resin condensation product formed from glycerine and tetrachlorophthalic acid, said resin having a thermometer drip point of more than 140 C., an average molecular weight of about 1000 and an acid number of less than 20, 40% to 60% by weight of the mixture of an epoxy polyester having two glycide moieties and at least one phthalic acid moiety and from 15% to 35% by weight of the mixture of the 1 to 1 adduct of dipentene and maleic acid anhydride, said three com ponents being the sole reactants, and heating the resulting mixture to temperatures of 100 to 200 C. for a few hours. 9. A heat hardenable resinous composition comprising 1) an alkyd resin wherein the alcohol component is entirely derived from alcohols having at least three hydroxy groups, (2) an epoxy polyester resin having essentially the structural formula wherein R and R are radicals selected from the group consisting of hydrogen, alkyl and aryl radicals, R and R are bivalent radicals selected from the group consisting of alkylene and arylene radicals and n is an integer from to 10, and (3) a dipentene:maleic acid anh dride adduct hardener, said three components being the sole reactants.
10. The composition of claim 9 wherein said epoxy polyester resin is present in amounts of from 40% to 60% by weight of the hardenable mixture.
11. The composition of claim 9 wherein said epoxy polyester resin is present in amounts of from 40% to 60% and said anhydride adduct hardener is present in amounts of from to 35 by weight of the hardenalble mixture.
12. A heat hardena-ble resinous composition comprising (1) a polyester resin condensation product formed from vglycerine and a phthalic acid, (2) an epoxy polyester resin having moglycide moieties and at least one phthalic acid moiety and (3) a dipentenezmaleic acid anhydride adduct hardener, said three components being the sole reactants.
13. A heat hardenable resinous composition comprising from 20% to by weight of the mixture of a polyester resin condensation product formed from glycerine and a phthalic acid, from 40% to by weight of the mixture of an epoxy polyester resin having two glycide moieties and at least one phthalic acid moiety and from 15% to 35% by weight of the mixture of a dipentenezmaleic acid anhydride adduct hardener, said three components being the sole reactants.
14. The composition of claim 13 wherein said adduct hardener is the distillation product of the condensation having a ratio of 1 mol of dipentene to 1 mol of maleic acid anhydride.
15. A heat harden-able resinous composition comprising from 20% to 40% by weight of the mixture of a polyester resin condensation product formed from glycerine and tetrachlorophthalic acid, sa-id resin having a thermometer drip point of more than C., an average molecular Weight of about 1000 and an acid number of less than 20, 40% to 60% by weight of the mixture of an epoxy polyester having two glycide moieties and at least one phthalic acid moiety and from 15% to 35 by weight of the mixture of the 1 to 1 adduct of dipentene and maleic acid anhydride, said three components being the sole reactants.
16. The hardened resin produced by the process of claim 1.
References Cited in the file of this patent UNITED STATES PATENTS 2,591,539 Greenlee Apr. 1, 1952 2,691,004 Doyle Oct. 5, 1954 2,712,535 Fisch July 5, 1955 2,781,333 Updegraflf Feb. 12, 1957 2,887,459 Carmody May 19, 1959 2,908,660 Belanger Oct. 13, 1959 FOREIGN PATENTS 944,995 Germany June 28, 1956
Claims (1)
- 9. A HEAT HARDENABLE RESINOUS COMPOSITION COMPRISING (1) AN ALKYD RESIN WHEREIN THE ALCOHOL COMPONENT IS ENTIRELY DERIVED FROM ALCOHOLS HAVING AT LEAST THREE HYDROXY GROUPS, (2) AN EPOXY POLYESTER RESIN HAVING ESSENTIALLY THE STRUCTURAL FORMULA
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE3052647X | 1957-11-22 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3052647A true US3052647A (en) | 1962-09-04 |
Family
ID=8085333
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US759139A Expired - Lifetime US3052647A (en) | 1957-11-22 | 1958-09-05 | Heat hardenable composition comprising an alkyd resin, an epoxy polyester resin, anda dipentene:maleic acid anhydride adduct and process of preparing same |
Country Status (1)
Country | Link |
---|---|
US (1) | US3052647A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3361694A (en) * | 1963-12-16 | 1968-01-02 | Avisun Corp | Process of preparing aqueous coating compositions useful for coating polypropylene films |
US4038339A (en) * | 1975-09-16 | 1977-07-26 | Westinghouse Electric Corporation | Epoxy-vinyl-polyester cold blended resin composition |
US4356285A (en) * | 1980-09-19 | 1982-10-26 | Hitachi Chemical Co., Ltd. | Thermosetting resin composition |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2591539A (en) * | 1950-10-03 | 1952-04-01 | Devoe & Raynolds Co | Resinous compositions |
US2691004A (en) * | 1951-10-31 | 1954-10-05 | Gen Electric | Oil-modified acidic polyester-ethoxyline resinous compositions |
US2712535A (en) * | 1949-08-12 | 1955-07-05 | Ciba Ltd | Elastic infusible products from epoxy compounds and cross-linking agents |
DE944995C (en) * | 1954-07-31 | 1956-06-28 | Henkel & Cie Gmbh | Process for the production of epoxy compounds |
US2781333A (en) * | 1952-09-10 | 1957-02-12 | American Cyanamid Co | Polymerizable compositions containing polyglycidyl esters of polycarboxylic acids |
US2887459A (en) * | 1955-10-17 | 1959-05-19 | Socony Mobil Oil Co Inc | Mixed resinous esters of oil-modified alkyd resins and of partially-esterified epoxide resins |
US2908660A (en) * | 1956-06-11 | 1959-10-13 | Devoe & Raynolds Co Inc | Polyepoxide polyalkylene glycol-anhydride compositions and processes for their preparation |
-
1958
- 1958-09-05 US US759139A patent/US3052647A/en not_active Expired - Lifetime
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2712535A (en) * | 1949-08-12 | 1955-07-05 | Ciba Ltd | Elastic infusible products from epoxy compounds and cross-linking agents |
US2591539A (en) * | 1950-10-03 | 1952-04-01 | Devoe & Raynolds Co | Resinous compositions |
US2691004A (en) * | 1951-10-31 | 1954-10-05 | Gen Electric | Oil-modified acidic polyester-ethoxyline resinous compositions |
US2781333A (en) * | 1952-09-10 | 1957-02-12 | American Cyanamid Co | Polymerizable compositions containing polyglycidyl esters of polycarboxylic acids |
DE944995C (en) * | 1954-07-31 | 1956-06-28 | Henkel & Cie Gmbh | Process for the production of epoxy compounds |
US2887459A (en) * | 1955-10-17 | 1959-05-19 | Socony Mobil Oil Co Inc | Mixed resinous esters of oil-modified alkyd resins and of partially-esterified epoxide resins |
US2908660A (en) * | 1956-06-11 | 1959-10-13 | Devoe & Raynolds Co Inc | Polyepoxide polyalkylene glycol-anhydride compositions and processes for their preparation |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3361694A (en) * | 1963-12-16 | 1968-01-02 | Avisun Corp | Process of preparing aqueous coating compositions useful for coating polypropylene films |
US4038339A (en) * | 1975-09-16 | 1977-07-26 | Westinghouse Electric Corporation | Epoxy-vinyl-polyester cold blended resin composition |
US4356285A (en) * | 1980-09-19 | 1982-10-26 | Hitachi Chemical Co., Ltd. | Thermosetting resin composition |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US2712535A (en) | Elastic infusible products from epoxy compounds and cross-linking agents | |
US2456408A (en) | Synthetic drying compositions | |
US2683131A (en) | Acidic polyester-ethoxyline resinous compositions | |
US2744845A (en) | Chlorinated maleic adduct-ethoxyline resinous compositions | |
US3089863A (en) | Process for preparation of a polyester resin of pentaerythritol, a dicarboxylic acid anhydride, and a monoepoxide | |
US3979477A (en) | Composition of epoxide resins, polycarboxylic acid anhydrides and polyester-dicarboxylic acids | |
US2592560A (en) | Polyepoxide compositions | |
US3985825A (en) | Adducts, containing epoxide groups, based on polyesterdicarboxylic acids | |
US2691004A (en) | Oil-modified acidic polyester-ethoxyline resinous compositions | |
US2504518A (en) | Synthetic drying compositions | |
US2653141A (en) | Partial esters of polyhydroxyl polyethers | |
US3219602A (en) | Triethanolamine borate catalyzed condensation of bis-phenol a glycidyl ethers with polymeric fat acids | |
US2890195A (en) | Compositions comprising a diepoxide and a polyhydric compound | |
US3035001A (en) | Epoxy ether compositions | |
US2908660A (en) | Polyepoxide polyalkylene glycol-anhydride compositions and processes for their preparation | |
US2947712A (en) | Epoxide resin compositions | |
US3052647A (en) | Heat hardenable composition comprising an alkyd resin, an epoxy polyester resin, anda dipentene:maleic acid anhydride adduct and process of preparing same | |
US2909496A (en) | Reaction products of polyepoxides and monomeric partial esters of polyhydric alcohols with maleic anhydrideunsaturated organic acid adducts, and methods and compositionsfor producing the same | |
US3937751A (en) | Curable compositions based on epoxide resins and polyester-tricarboxylic acids or -tetracarboxylic acids | |
US4478994A (en) | Use of unsaturated polyesters as additive binders improving adhesion in coating agents for coating of metals | |
US2934506A (en) | Modified epoxide resins | |
US2962469A (en) | Polymerizable compositions containing dicyclopentadiene dioxide and plycarboxylic acid and resins prepared therefrom | |
US2921925A (en) | Polyepoxide compositions | |
US3291858A (en) | Thermosetting resin based paints containing a polyester prepared by reacting phthalic anhydride, glycerol, and glycidyl esters of alpha-branched saturated monocarboxylicacids with either an amide-aldehyde or a phenolaldehyde resin | |
US3277035A (en) | Modified alkyd resins containing glycidyl esters of mixed alpha-branched saturated aliphatic monocarboxylic acids |